Treatment of textile materials



TREATMENT or TEXTILE MATERIALS George E. Niles, Winchester, Massg, "assignortdMonsanto Chemical Company, St. Louis,"M0.,- a cor orationof 'Belaware No Drawing, Application February 24,1951, Serial N0. "212,697

2 Eiaims. i(Cl. 117-4395) This invention relatesto'improved textile finishing'nia- .terials, and methodsof treating yarns and fabrics therewith.

It is common practice to treat yarns and fabrics with starch solutions in order to impart a relatively stiffened finish thereto. Starched fabrics however lose their stiffuened character and appearance after a' singlmwashing,

:and alsotend to dust out.

Furthermore, fabrics treated with starch finishes will not retain the StlfieIlBd"-filllSh after mild washings.

It is the primary object of the -presentinventionfto provide a substantially permanent stii'fenedfinishfwhich cannot be appreciably removed by ordinary washing operations and is substantially-free of dusting.

.Still further objects and advantages-. ofthe invention will appear from the following-description and. appended claims.

In accomplishing the above objectsthe yarn or fabric is treated, as by dipping-or spraying, with an -aqueous solution or dispersion of an alkali or amine salt, including sodium, potassium, ammonium and quaternary-ammonium salts of copolymerized styrene-maleic anhydride, after which the yarn is treated with a-=dilute solution of a metal salt. The treated fabric is then dried, whereby an insoluble salt of thecopolymer is formed, which remains on the fabric after Washing and provides a substantially permanent :finish.

Suitable ammonium or amine salts ofthe copolymer include the salts of ammonia,

guanidine, 'al-kylamines,

such as'methyl, butyl and arnyl amine, andz'quaternary =ammonium hydroxides, such 'asphenyl .triniethyl ammonium hydroxide.

The concentration of the styrene-maleie salt solution and the pick-up should 'be adjusted to depositonthe fabric from 2 to 15% byweight of the styrene-maleicgsalt,

but preferably between about 4 and 7%. The r'netallsalt solution employed is generallydilute, asonly small sec- .tions of cloth are sub ected to thissolution at any-one time. the solution may be varied in accordance with the con- Moreover, the timeof immersionof theicloth in centration. In general, solutions of 'about 1 to -2% strength are used, but stronger solutions may be employed, if desired.

' If the metal salt is water-soluble, it may be applied to the fabric before the salt of the anhydride is-applied,

.or after the salt of the anhydride is applied but before ,drying, .or it may be applied after'thesaltof-the anhydride is applied and dried. I

lncases in which the metal salt is insolublejin water,

.these salts are first dispersed in the aqueousba-th of the salt of the anhydride before beingapplied. In such instances from S-to 30% by weight of 'the' Water-soluble metal salt, based on the weight of the salt of the anhydride in the bath, is generally used. "'Be'st 're'sults are obtained by using from 1 to 30% by weight .of the'waterinsoluble metal salt based on the weight of'the"salt of soluble metal salt and the :salt'of-the copolymer is-supplied, in general, in an amount sufiicient toprovidefrom about 1 to 10% by weight of the'salt'of the-c p Iymer, based on the fabric or yarn, and from =to- 30%; by weight of the-water-insoluble metal .salt, based onsthe United States Patent'() 2 weight ofhthe salt of the copolymerqapplied. -Best're- *sultsare obtained .by applying from 1 to 7%"by-weight "of the salt of the copolymer,-based on the fabric or yarn,

and-froml0 to 30%':by-weight of the water-insoluble yarn "which is dried at the lower temperatures.

-The metal salts which maybe used for the purpose --of-this invention are salts of aluminum, antimony, -ar- -senic,-barium,- beryllium, bismuth, cadmium, calcium, cerium, cesium, chromium, cobalt, copper, iron, lead, magnesium, manganese, mercury, molybdenum, nickel, platinum, silver, strontium, tin, zinc and zirconium. A large -variety of Water-insoluble metal salts areuseful in-the'compositionsand methods 'of this invention. One particularly suitable class of'water-insoluble salts-are the water-insoluble salts of metals of Group II -A of the;periodictable, that is, water-insoluble salts of beryllium suchas berylliumcarbonate, Water-insoluble salts of magnesium such as magnesium pyrophosphate,-t ribasic magnesium phosphate andthe like and water-insoluble salts of calcium and barium such as calcium or barium -'carbonate, oxalate, triphosphate, sulfate and the'like. The water-insoluble salts, and particularly the water- "insoluble carbonates, of-Group II A metalsare preferred.

-It is alsopossible to use water-insoluble salts of metals of Group llB of the periodic table, that is, water-insoluble'saltsof zinc, cadmiumand mercury. As examples of 'such"'salts=,may.--be mentioned the oxalates and tribasic "phosphatesof these metals including the'mercuric and --mercurous* compounds, zinc and cadmium carbonate, inkercurous carbonate, basic mercuric carbonate and the *1 e.

Water insoluble salts of metals of Group I B of the periodic table,-that is, water-insoluble salts ofcopper, silverand gold are generally suitable. As examples oi suchsalts may be mentioned basic cupric carbonate, tribasic'cupric phosphate, cupric oxalate, cuprous carbonate, silver -pyrophosphate, silver carbonate-and -the -like. 1 The use of water-insoluble salts of copper j is particularly advantageous since-such salts react'w'ith the salt of the copolymer on drying on the material to form an insoluble finish on the material consisting of the copper salt of the copolymer which is not only resistant to laundering but is also resistance to "fungus and bacteria.

It is also possible in accordance with this invention "to"u'se'water insoluble salts of metals of Group III A Tof-"the 'p'eri'odictable, for example, the Water-insoluble salts of aluminum, As examples of suitable water-insoluble aluminum salts maybe mentioned aluminum-oxittllatefkaluminum phosphate, basic aluminum acetate and In general, the water-insoluble salts of metals of roup 'I'V'Aand IVB of the periodictable areuseful. T-hus, itispossible to use such water-insoluble-he'avy :metal saltsets basic zirconiumoxalate, titanium sulfate -[Ti2 (SO4")-3], st-annicphosphate andthe like.

it-"is atso'possible to use water-insoluble salts of the metals of Group VlII of the periodic table, that is, waterinsolu-ble salts of iron, cobalt and nickel. As examples of suchwat'e'rinsoluble salts may be mentioned basic ferric 'acetate, ferricpyrophosphate, ferric phosphate, cobaltous carbonate, cobaltous phosphate, nickelcarbonate, basic nickel carbonate, nickel phosphate, nickel oxalate and the like.

. The copolymer of styrene and maleic anhydride used in accordance W'ithfthis invention is a well established product 'which may be prepared in several ways. One of the welbk'nown methods is mass polymerization; which involves heat'ing'styrene and maleic anhydride at tem- .Peratures between about and"300 F. for several hours or more. Preferably, the materials are heated cautiously, as in a water bath. Another method which may be used is known as the solvent process which involves reacting the styrene and maleic anhydride at slightly elevated temperatures in the presence of a solvent which is capable of dissolving both the starting materials and the finished polymer, such as acetone. If desired, the copolymerization may be carried out in the presence of a catalyst, such as benzoyl peroxide. Still another method which can be used is the solvent-non-solvent method which involves carrying out the reaction as above, but in a solvent which is capable of dissolving only the starting material and not the final copolymer.

The copolymer of styrene and maleic anhydride produced by the above or by any other well-known method of manufacture is soluble in acetone, but insoluble in alcohol or benzene, and forms water-soluble salts of ammonia or alkali metals. Instead of styrene, substituted styrenes, such as methyl or butyl styrene, chlorostyrene or the like, may be used to prepare copolymers which are soluble in dilute aqueous solutions of alkali or ammonia. Instead of maleic anhydride, partially esterified maleic anhydride, such as the half ester of isopropyl maleate, may be used. It is also possible to prepare and use in accordance with this invention copolymers of styrene and maleic anhydride which have been copolymerized with relatively small amounts of other unsaturated compounds, such as vinyl acetate, vinyl chloride, vinyl ethyl ether, indene, vinyl methyl ketone, acrylic esters and the like.

A further understanding of the invention will be obtained from the following examples, the parts being given by weight.

Example I A solution of an ammonium salt of a styrene-maleic anhydride resin was prepared by mixing together 600 parts of styrene-maleic anhydride, prepared by copolymerizing equimolecular quantities of styrene and maleic anhydride at about 200 F. in a water bath, 400 parts of 26% NH4OI-I and 9000 parts of water. The resulting mixture was then heated to 200 to 212 F. with stirring, and maintained at this temperature until a uniform, somewhat viscous transparent solution resulted. This required about one hour.

Spun rayon fabric and heavy cotton sheeting were dipped in the bath prepared as described above, after -which it was passed through a padder adusted for 100% pick-up. The bath was maintained at about 120 F. during the treatment to insure uniform penetration. The treated sheeting was then dried, after which the dried sheeting was immersed in a 2% zirconium oxychloride solution for minutes at 120 F. Following this the treated fabric was thoroughly rinsed and dried. The finished fabric was resistant to washing and showed good water-repellency.

Example II Samples of spun rayon fabric and cotton fabric treated with ammonium salt solutions prepared as described in Example I were treated with 1% solutions of aluminum formate, copper acetate and antimony chloride respectively for 10 minutes at 120 F. The fabrics were then thoroughly rinsed and dried. The treated fabrics had a full firm hand and were resistant to washing.

Example Ill One thousand parts of a 7% aqueous solution of the ammonium salt of the copolymer of styrene and maleic anhydride were mixed with parts of powdered CaCOs and ball milled for 24 hours. Samples of spun rayon and cotton sheeting were immersed in the dispersion thus prepared and then padded, the pad being adjusted to deposit on the fabric 7% solids. The treated fabrics were then dried at 200 F. for 5 minutes and cured for 5 minutes at 280 F. The resulting fabrics were resistant to washing and had a stiff finish.

Example IV One thousand parts of a 7% aqueous solution of the ammonium salt of the copolymer of styrene and maleic anhydride and 20 parts of powdered zinc carbonate were stirred vigorously to form a dispersion of the zinc carbonate in the copolymer salt solution. A spun viscose rayon fabric was immersed in the resulting dispersion ill immediately after the dispersion had been prepared and the fabric was then squeezed between pad rolls using a pressure of pounds per linear inch on the rolls. The fabric was then framed and dried at 200 F. for 30 minutes. The resulting fabric had a stiff finish which was resistant to laundering.

Example V One thousand parts of a 7% aqueous solution of the ammonium salt of the copolymer of styrene and maleic anhydride and 20 parts of powdered ferric phosphate were stirred vigorously to form a dispersion of the ferric phosphate in the copolymer salt solution. A spun viscose rayon fabric was immersed in the resulting dispersion immediately after the dispersion had been prepared and the fabric was then squeezed between pad rolls using a pressure of 160 pounds per linear inch on the rolls. The fabric was then framed and dried at 200 F. for 30 minutes. The dried fabric had a crisp, stiff finish which was not materially altered by washing with a 1% soap solution for 5 minutes.

Example VI One thousand parts of a 7% aqueous solution of the ammonium salt of the copolymer of styrene and maleic anhydride and 20 parts of powdered aluminum phosphate were stirred vigorously to form a dispersion of the aluminum phosphate in the copolymer salt solution. A spun viscose rayon fabric was immersed in the resulting dispersion immedaitely after the dispersion had been prepared and the fabric was then squeezed between pad rolls using a pressure of 160 pounds per linear inch on the rolls. The fabric was then framed and dried at 200 F. for 30 minutes. The resulting fabric had a stiff finish which was resistant to washing.

Although the examples refer to the treatment of cotton and viscose fabrics, the process is also applicable to acetate rayon, nylon, glass, linen, flax, hemp, jute, ramie, wool, silk, cuprammonium rayon and synthetic protein fabrics, and fabrics containing mixtures and blends of any of the above materials.

By treating fabrics with the finishing agents described herein, a substantially permanent, stiffened finish is obtained, due to the fact that only relatively small amounts of the dried and reacted resin are lost on washing, i. e. of the order of 2 to 10%. The finished fabric is also smooth and substantially free of dusting in contrast to the well-known starch treated fabrics. When the resin is applied to the warp yarn and insolubilized thereon, there is the further advantage that the weaving operation is improved owing to the higher tensile strength of the yarn, its increased resistance to abrasion, and its generally stiffened character. The fabric prepared from treated yarn has the desired finish characteristics without further treatment, but if desired it may be subjected to additional finishing operations. The styrene-maleic salt may also be applied to the yarn without insolubilization, after which the yarn is woven, and the metal salt solution is applied.

It is customary to apply the sizing or finishing materials described herein to yarns or fabrics. However, it is possible to obtain similar results by treating fibers, either initially or at any stage of their processing prior to spinning, after which the fibers may be spun and woven to obtain fabrics of the desired finish characteristics. Yarns prepared from such treated fibers may also be readily woven. It is also possible to treat in accordance with this invention fibers which are to be used as such, as for example in cotton batting, or in the preparation of non-woven fabrics.

It is believed that the insolubility, resistance to washing and water-repellency of fabrics treated according to this invention are due to the metathesis of the metal ion for the ammonium or alkali ion in the salt of the styrenemaleic anhydride copolymer. This exchange may take place before, during or after the drying operation.

It should be understood that the aqueous solutions referred to in the appended claims are intended to include aqueous dispersions, as it is possible that the ammonium or amine salts in the solution are actually present in the form of a colloidal dispersion.

This application is a continuation-in-part of my. copending application Serial No. 770,943, filed August -27,

1947, now U. S. Patent No. 2,586,477 issued February 19, 1952.

What is claimed is:

1. The method of finishing a textile material which comprises treating the material with an aqueous dispersion of (1) a salt of a copolymer of a substance selected from the group consisting of styrene, methyl styrene, butyl styrene and chlor styrene with a substance selected from the group consisting of maleic anhydride and the half ester of isopropyl maleate, said salt being selected from the group consisting of alkali and amine salts, and (2) from about 5 to 30% by weight, based on the salt of the copolymer, of calcium carbonate, said dispersion being supplied in an amount sufiicient to provide from about 1 to by Weight of the salt of the copolymer, based on the material, and from about 5 to 30% by Weight of said calcium carbonate based on the salt of the copolymer, and then drying the material at a temperature of 180 to 300 F. to form the insoluble calcium salt of said copolymer.

2. The method of finishing a textile material which comprises treating the material with an aqueous dispersion of an ammonium salt of a copolymer of styrene and maleic anhydride and from about 5 to by Weight, based on said ammonium salt, of calcium carbonate, said dispersion being supplied in an amount sufiicient to provide from about 1 to 10% by Weight of said ammonium salt, based on the material, and from about 5 to 30% by weight of said calcium carbonate, based on the ammonium salt thus applied, and then drying the material at a temperautre of to 300 F. to form the insoluble calcium salt of said copolymer.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,976,679 Fikentscher et al Oct. 9, 1934 2,356,879 Pense et al Aug. 29, 1944 OTHER REFERENCES Hackhs Chemical Dictionary, 3rd ed., Blackiston, Philadelphia (1944), p. 344. 

1. THE METHOD OF FINISHING A TEXTILE MATERIAL WHICH COMPRISING TREATING THE MATERIAL WITH A AQUEOUS DISPERSION OF (1) A SALT OF COPOLYMER OF A SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF STYRENE, METHYL STYRENE, BUTYL STYRENE AND CHLOR STYRENE WITH A SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF MALEIC, SAID ANHYDRIDE AND THE HALF ESTER OF ISOPROPYL MALEATE, SAID SALT AMINE SALTS, AND (2) THE GROUP CONSISTING OF ALKALI AND AMINE SALTS, AND (2) FROM ABOUT 5 TO 30% BY WEIGHT, BASED ON THE SALT OF THE COPOLYMER, OF CALCIUM CARBONATE, SAID DISPERSION BEING SUPPLIED IN AN AMOUNT SUFFICIENT TO PROVIDE FROM ABOUT 1 TO 10% BY WEIGHT OF THE SALT OF THE COPOLUMER, BASED ON THE MATERIAL, AND FROM ABOUT 5 TO 30% BY WEIGHT OF SAID CALCIUM CARBONATE BASED IN THE SALT OF THE COPOLYMER, AND THEN DRYING THE MATERIAL AT A TEMPERATURE OF 180 TO 300 F. TO FORM THE INSOLUBLE CALCIUM SALT OF SAID COPOLYMER. 